JPH07140472A - Spacer for liquid crystal display plate and liquid crystal display plate using the same - Google Patents

Abstract

PURPOSE:To provide a spacer for a liquid crystal display plate which is capable of strictly maintaining a specified spacing distance in spite of a drastic decrease in the number of pieces to be sprayed as compared with the conventional org. polymer particles without flawing of electrode substrate surfaces, generation of low-temp. foaming, generation of unequal images, increase of costs and degradation in various kinds of display performance and enables the production of the high-performance liquid crystal display plate having excellent image quality and the liquid crystal display using this spacer. CONSTITUTION:The spacers 3, 8 for the liquid crystal display plate are the spacers for the liquid crystal display plate consisting of org.-inorg. composite particles essentially consisting of a polysiloxane having the org. silicon formed by chemical bonding of at least one piece of carbon atoms in the org. group directly to a silicon atom within the molecule. The modulus of elasticity in 10% compression of the particles is 350 to 3000kg/mm<2>, the residual displacement after 10% deformation is 0 to 5%, the average particle size is 0.5 to 50mum and the coefft. of fluctuation of the particle size is <=20%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spacer for a liquid crystal display panel, which has very uniform particle diameters and has a compressive elastic modulus and a residual displacement in a specific range. This invention also
The present invention relates to a liquid crystal display panel in which pixel defects and low-temperature bubbling due to image unevenness and TFT disconnection hardly occur, and the number of spacers interposed between electrode substrates is reduced.

[0002]

2. Description of the Related Art A liquid crystal display plate (LCD: also called a liquid crystal display element) is constructed by interposing a spacer between two opposing electrode substrates and sandwiching a liquid crystal substance in the gap. The spacer is used to keep the thickness of the liquid crystal layer uniform and constant, and is used as an in-plane spacer in the liquid crystal layer and a seal portion spacer in the peripheral adhesive sealing material.

In a liquid crystal display panel, a peripheral sealing material in which a seal spacer is dispersed and an in-plane spacer are sandwiched between two opposing electrode substrates, and both electrode substrates are held at the curing temperature of the peripheral sealing material. It is made through a process of hot pressing and fixing. In general, a spacer for a liquid crystal display panel is very expensive, so it is desirable to use the spacer as little as possible. In particular, when using in-plane spacers that are in direct contact with the liquid crystal substance, in order to minimize elution from the interior of the spacers into the liquid crystal, such as ions and molecules that adversely affect the display performance of the liquid crystal display plate, The amount used should be as low as possible.

Generally, the display performance required for practical use of liquid crystal display panels is high-speed response, high contrast,
Wide viewing angle and the like can be mentioned. In order to realize these various performances, the thickness of the liquid crystal layer, that is, the gap distance between the two electrode substrates must be kept strictly constant. As a spacer for a liquid crystal display panel that meets such a demand, a sol-
Silica particles produced by the gel method (JP-A-62-26993).
3), a product obtained by firing the silica particles (JP-A-1
No. 234826), styrene-based polymer particles obtained by suspension-polymerizing styrene-based monomers and the like, and all of them are spherical particles having a narrow particle size distribution and a very uniform particle size.

In order to make the gap distance strictly constant, it is necessary not only to use particles having such uniform particle diameters as spacers, but also to finely adjust the gap distance.

[0006]

However, in the prior art, there were the following problems, and it was not possible to obtain a spacer for a liquid crystal display panel capable of controlling the hardness of particles and the mechanical recoverability. The one obtained by firing silica particles produced by the sol-gel method has poor deformability and is extremely hard as a material, so when a press is performed to produce a liquid crystal display plate, a vapor deposition layer such as electrodes on the substrate, orientation Physical damage is given to the coating layer such as a film and a color filter, and a pixel defect occurs due to image unevenness and TFT disconnection. Further, since the difference in the coefficient of thermal expansion between the silica calcined product particles and the liquid crystal is large, a liquid crystal display panel using the silica calcined product particles has, for example, a minus 40.
When exposed to a low temperature environment of ℃, the particles do not shrink to the extent that the liquid crystal shrinks, creating a gap between the liquid crystal layer and the electrode substrate, and the display function does not work at all. Occurs.

The silica particles produced by the sol-gel method are
Since it is softer than the particles of calcined silica, it does not cause the physical damage even if it is deformed by the press. But,
This unsintered silica particle is inferior in mechanical restoration,
The gap distance becomes non-uniform and image unevenness is likely to occur. This is because the degree of deformation of the spacer due to the pressing is non-uniform, so that if the spacer is inferior in mechanical recovery, the particle size of the spacer after pressing becomes non-uniform. Moreover, uncalcined silica particles cause a problem of low temperature foaming, similar to particles of calcined silica.

Since styrene-based polymer particles are organic particles and are very soft as a raw material, in order to reduce the pressure applied to individual particles in the pressing process for fine adjustment of the electrode substrate gap distance, the deformation is reduced. There is no choice but to increase the number of sprays. This is because when the pressing process is performed with a small number of sprays, the amount of deformation increases because the pressure applied to each particle increases, and the mechanical resilience to make the electrode substrate gap distance after pressing uniform and uniform. Because I can't get it. Therefore, not only the manufacturing cost is increased, but also the area of the part where the image is not formed is increased, and further, the amount of impurities such as ions and molecules eluted from the inside of the spacer into the liquid crystal layer is increased. It causes deterioration of various display qualities such as deterioration of contrast and increase of roughness.

The present invention has a hardness between the calcined silica particles and the organic particles, which is necessary for avoiding the above-mentioned problems, and is necessary for maintaining a uniform gap distance. An object of the present invention is to provide a spacer for a liquid crystal display panel that also has mechanical recoverability. This invention also uses such a spacer for a liquid crystal display panel to
Physical damage during manufacturing of electrode substrate, low temperature foaming, image unevenness,
It is an object of the present invention to provide a liquid crystal display panel that is less likely to cause a decrease in contrast and roughness.

[0010]

In order to solve the above-mentioned problems, the present invention mainly relates to a polysiloxane having in its molecule an organosilicon in which at least one carbon atom in an organic group is directly chemically bonded to a silicon atom. A spacer for a liquid crystal display panel, comprising organic-inorganic composite particles as a component, wherein the particles have a 10% compression elastic modulus of 350 to 3000 kg / m.
m ² , the residual displacement after 10% deformation is 0 to 5%, the average particle diameter is 0.5 to 50 μm, and the variation coefficient of the particle diameter is 20% or less (hereinafter, a spacer for a liquid crystal display panel). , Sometimes referred to as “first spacer”).

The present invention also provides the following general formula (1)

[0012]

[Chemical 2]

(In the formula, R ¹ is an optionally substituted alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an unsaturated aliphatic group having 2 to 10 carbon atoms. A monovalent group selected from the group consisting of residues, R ² is a monovalent group selected from a hydrogen atom, an alkyl group having 1 to 5 carbon atoms and an acyl group having 2 to 5 carbon atoms, and m is 0 to 3 Indicates an integer, m is 2
In the case of, the two R ¹ may be different from each other or may be the same. When m is 3, three R ¹ 's may be different from each other, or two or more R ¹ 's may be the same. If 4-m is 2,
The two OR ² may be different from each other or may be the same. When 4-m is 3, three OR ^{2 s} may be different from each other or two or more may be the same. When 4-m is 4, four OR ^{2 s} may be different from each other or two or more may be the same. ) At least one hydrolyzable / condensable silicon compound selected from the group consisting of the compound represented by the formula (1) and the derivative thereof (provided that the silicon compound which can be used alone is a compound represented by m = 1 in the formula (1) and Only the compound selected from the group consisting of its derivatives, and the silicon compound used in combination of two or more,
Both a compound selected from the group consisting of a compound represented by m = 1 in Formula (1) and a derivative thereof, a compound selected from the group consisting of a compound represented by m = 0 in Formula (1) and a derivative thereof, or Must include either one. ] Hydrolyzable / condensable metal compound containing
Provided is a spacer for liquid crystal display panel (hereinafter sometimes referred to as "second spacer") obtained by heat treatment in the range of 000 ° C.

In order to solve the above problems, the present invention also provides a liquid crystal display panel using the spacer for liquid crystal display panel of the present invention as a spacer interposed between electrode substrates. As the spacer for a liquid crystal display panel of the present invention, at least one selected from the above-mentioned first spacer and second spacer can be used.

First, the first spacer of the present invention will be described. The polysiloxane referred to in the present invention is represented by the following formula (2)

[0016]

[Chemical 3]

It is defined as a compound in which a siloxane unit represented by the formula (3) is chemically bonded continuously to form a three-dimensional network. The organic group as used in the present invention has 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and at least one carbon atom is directly chemically bonded to one or more hydrogen atoms.
It is at least one selected from divalent, divalent and trivalent groups. As the organic group, a group consisting of an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 10 carbon atoms, and an unsaturated aliphatic residue having 2 to 10 carbon atoms. A monovalent group selected from the group consisting of alkyl groups having 1 to 5 carbon atoms, which may have a substituent, and unsaturated aliphatic residues having 2 to 5 carbon atoms (for example, vinyl group, allyl group). , An ethynyl group and a propynyl group) are more preferred. These organic groups have the advantages that they are cheaper, easier to obtain, and easier to handle than organic groups other than these. Here, the substituent which the alkyl group may have is, for example, a glycidoxy group, a mercapto group, an amino group or the like, and one to all of the hydrogen atoms of the alkyl group may be substituted, preferably one of the hydrogen atoms. To replace ~ 3. Specific examples of the organic group include, for example, methyl, ethyl, propyl, butyl,
Vinyl, 3-glycidoxypropyl, 3-mercaptopropyl, 3- (2-aminoethylaminopropyl), phenyl and the like.

The term "organosilicon" as used in the present invention means that at least one carbon atom in an organic group is directly chemically bonded to at least one silicon atom contained in the siloxane unit. The organic group is 1 to 3 per silicon atom.
Can be chemically bonded individually. The organic-inorganic composite particles mainly composed of polysiloxane having organosilicon in the molecule as referred to in the present invention have the inorganic constitutional unit represented by the above formula (2) and the organosilicon at the same time. It is a particle that has both a large hardness that is a characteristic and a high mechanical resilience that is an organic characteristic. here,
The hardness and the mechanical resilience are measured by compression elastic modulus and residual displacement, respectively, which will be described in detail later. In order to satisfy the above-mentioned 10% compressive elastic modulus and the range of residual displacement after 10% deformation, the proportion of polysiloxane having organosilicon in the molecule in the organic-inorganic composite particles is 70% by weight or more. Preferably 10
It is more preferably 0% by weight. Examples of components other than polysiloxane having organosilicon in the molecule include oxides of boron, aluminum, gallium, indium, phosphorus, titanium, zirconium and the like.

The 10% compressive elastic modulus referred to in the present invention is a value measured by the following measuring method. Shimadzu micro compression tester (MCTM-200 manufactured by Shimadzu Corporation)
Sample table (material: SKS flat plate) at room temperature (25 ° C)
Using a circular flat plate indenter (material: diamond) having a diameter of 50 μm, a load is applied to the center of the particle at a constant load speed for one sample particle scattered up to a compression displacement of 10% of the particle diameter. The particles are deformed and the load and the number of millimeters of compressive displacement at 10% deformation are determined. Calculate the calculated compression load, particle compression displacement, and particle radius as

[0020]

[Equation 1]

[Where, E: compressive elastic modulus (kg / mm ² ), F: compressive load (kg), K: Poisson's ratio of particles (constant, 0.38) S: compressive displacement (mm) R: radius of particles (Mm). ] The compressive elastic modulus calculated by substituting into] is 10% compressive elastic modulus. Immediately thereafter, the load is removed at the same speed as when the load is applied, and the load is finally removed until the load becomes zero, and the size of the deformation still remaining in the particles is obtained. The residual displacement is calculated as a percentage of the particle size. This operation is performed for 3 different particles, and the average value is 10% of the particles.
The compressive elastic modulus and the residual displacement are used as the scale of particle hardness and mechanical resilience, respectively.

When the 10% compressive elastic modulus of the conventional spacer particles is measured by the above measuring method, the calcined silica particles are 4400 kg / mm ² , and the styrene polymer particles are 300.
It was kg / mm ² . In contrast, the first spacer of the present invention has a 10% compression elastic modulus of 350 to 3000 kg / mm.
^2, preferably in the range from 550~2500kg / mm ^2, and is adjusted to any hardness within a range more preferably of 550~2000kg / mm ^2. If the 10% compressive elastic modulus is less than the above range, there are problems such as an increase in manufacturing cost due to an increase in the number of dispersed spacer particles, a decrease in contrast, and an increase in roughness as described above. However, there are problems such as physical damage to the adhesive layer and coat layer on the substrate and low temperature foaming.

Regarding the residual displacement after 10% deformation, the unsintered silica particles had a residual displacement of 8%.
The first spacer of the present invention is a composite particle having a residual displacement in the range of 0 to 5%, preferably in the range of 0 to 4% and excellent mechanical recoverability. If the residual displacement after 10% deformation exceeds the above range, there is a problem that image unevenness occurs as described above.

The 10% compressive elastic modulus and the degree of residual displacement in the above range are achieved by adjusting the ratio of the organic groups in the particles. For example, increasing the proportion of organic groups reduces the 10% compressive modulus and residual displacement,
When the ratio of the organic group is lowered, the compressive elastic modulus of 10% and the residual displacement are increased. The proportion of the organic group in the first spacer of the present invention is usually 5 to 17% by weight, preferably 7 to 1 by weight, based on the weight of all carbon atoms.
It is 7% by weight. The reason is that when the organic group is less than the above range, the compressive elastic modulus and the residual displacement become large, the particles become too hard, or sufficient mechanical restoration cannot be obtained, and when the number is large, On the contrary, the compression modulus becomes too small, and the particles become softer than necessary. When the amount of the organic group is within the above range, more effective hardness and mechanical resilience are obtained in order to avoid the above-mentioned problems.

The average particle diameter of the first spacer of the present invention can be arbitrarily produced depending on the size of the target gap distance, but is usually 0.5 to 50 μm, and 1
It is preferably ˜20 μm, more preferably 1 to 15 μm. If it is out of the above range, the practical gap distance of the liquid crystal display panel cannot be achieved, and it is a region that is not usually used as a spacer.

The coefficient of variation of the particle diameter of the first spacer of the present invention is 20% or less, preferably 10% or less, more preferably 8% or less from the viewpoint of uniformity of the gap distance. If the upper limit is exceeded, the uniformity of the gap distance is reduced and image unevenness is likely to occur. The coefficient of variation of particle size is

[0027]

[Equation 2]

Is defined by In the present invention, the average particle diameter and the standard deviation of the particle diameters are obtained from the following equations by actually measuring the particle diameters of 200 arbitrary particles in an electron microscopic image.

[0029]

[Equation 3]

Next, another liquid crystal display panel spacer (the second spacer) according to the present invention will be described. The first spacer can be manufactured by a method for manufacturing a second spacer described later. The compound represented by the general formula (1) used in the present invention has 1 to 4 hydrolyzable groups, and the hydrolyzable group is a hydroxyl group or an alkoxy group having 1 to 5 carbon atoms. , A monovalent group selected from an acyloxy group having 2 to 5 carbon atoms, and preferably a methoxy group, an ethoxy group, a propoxy group or an acetoxy group. These hydrolyzable groups are
It is used in the present invention because it can be hydrolyzed with water and then condensed to form a polysiloxane. The compound represented by the general formula (1) has m = 1 to 3
In the case of, it has the above-mentioned organic group (or the above-mentioned organosilicon) and is used for introducing the organic group into the resulting composite particles.

Specific examples of the compound represented by the general formula (1) used in the present invention are as follows. The compound represented by m = 0 is a tetraalkoxysilane compound such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane and dimethoxydiethoxysilane; a tetraacyloxysilane compound such as tetraacetoxysilane.

The compound represented by m = 1 is methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, trimethoxyvinylsilane, triethoxyvinylsilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-
Examples include organotrialkoxysilane compounds such as (2-aminoethylaminopropyl) trimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltriacetoxysilane, and phenyltriacetoxysilane, and organotriacetoxysilane compounds.

The compound represented by m = 2 is a diorganodialkoxysilane compound such as dimethoxydimethylsilane, diethoxy-3-glycidoxypropylmethylsilane, dimethoxydiphenylsilane, diacetoxydimethylsilane and diphenylsilanediol. . The compound represented by m = 3 is triorganoalkoxysilane such as trimethylmethoxysilane, trimethylethoxysilane, acetoxytrimethylsilane, and trimethylsilanol.

Among the compounds represented by the general formula (1), organotrialkoxysilane compounds and tetraalkoxysilane compounds are more preferable starting materials. Further, as another hydrolyzable and condensable silicon compound, there is a derivative of the compound represented by the general formula (1). As an example, a compound in which a part of the hydrolyzable group is substituted with a carboxyl group, a β-dicarbonyl group or another group capable of forming a chelate compound, or these silicon compounds or chelate compounds are partially hydrolyzed There is a low condensate obtained by condensation.

The above-mentioned hydrolyzable / condensable silicon compounds may be used alone or in combination of two or more as a raw material (here, a hydrolyzable / condensable metal compound). it can. The above-mentioned silicon compound which can be used alone is only a compound selected from the group consisting of the compound represented by m = 1 in the formula (1) and its derivative, and when used alone, the second spacer of the present invention can be used only in this case. can get.

The silicon compound used in combination of two or more is
Both a compound selected from the group consisting of a compound represented by m = 1 in Formula (1) and a derivative thereof, a compound selected from the group consisting of a compound represented by m = 0 in Formula (1) and a derivative thereof, or Must include either one. The second spacer of the present invention can be obtained only in this case when two or more are used in combination. In this case, the mixing ratio of each silicon compound represented by m in the general formula (1) of 0, 1, 2, 3 and their derivatives is such that the average composition of the raw materials after mixing is the following general formula (3). It is preferable that n in is determined to be 0.5 to 1.

[0037]

[Chemical 4]

(In the formula, R ³ is the average composition of organic groups having carbon atoms directly bonded to silicon atoms, R ⁴ is hydrogen atom,
At least one 1 selected from an alkyl group and an acyl group
The average composition of valence groups is shown. ) When at least one selected from the silicon compound represented by the general formula (1) in which m is 2 and the silicon compound represented by m is 3, and derivatives thereof is used as a raw material, or m is represented by 0. In the case of using at least one selected from the silicon compounds and derivatives thereof as raw materials,
The second spacer of this invention cannot be obtained.

The hydrolyzable / condensable metal compound used to obtain the second spacer is represented by the above-mentioned general formula (1), which is a raw material of the polysiloxane component having the organosilicon in the molecule. Only a hydrolyzable / condensable silicon compound selected from the compound represented by the formula and a derivative thereof may be used, or the hydrolyzable / condensable silicon compound and boron, aluminum, gallium, indium, phosphorus, It is also possible to use a substance in which an organic metal compound such as titanium or zirconium or another metal compound capable of being hydrolyzed and condensed selected from an inorganic compound is allowed to coexist. These proportions are preferably determined such that the proportion of the polysiloxane in the composite particles is 70% by weight or more.

The above-mentioned hydrolyzable / condensable metal compound of the raw material is hydrolyzed and condensed in a solvent containing water. For the hydrolysis and condensation, any method such as batch, division, continuous, etc. can be adopted. Upon hydrolysis or condensation, a catalyst such as ammonia, urea, ethanolamine, tetramethylammonium hydroxide, alkali metal hydroxide or alkaline earth metal hydroxide may be used. In addition, water and an organic solvent other than the catalyst may be present in the solvent. Specific examples of the organic solvent include methanol, ethanol, isopropanol, n-butanol,
Alcohols such as isobutanol, sec-butanol, t-butanol, pentanol, ethylene glycol, propylene glycol, 1,4-butanediol;
Ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; (cyclo) paraffins such as isooctane and cyclohexane; ethers such as dioxane and diethyl ether; aromatic hydrocarbons such as benzene and toluene alone Alternatively, they are mixed and used.

For the hydrolysis and condensation, for example, the metal compound capable of being hydrolyzed / condensed from the above-mentioned raw material or an organic solvent solution thereof is added to a solvent containing water, and the temperature is in the range of 0 to 100 ° C., preferably 0 to 70 ° C. By stirring for 30 minutes to 100 hours. Further, the composite particles obtained by the above method may be charged as seed particles in a synthetic system in advance, and the above raw materials may be added to grow the seed particles.

Thus, the hydrolyzable / condensable metal compound containing the hydrolyzable / condensable silicon compound as the raw material is hydrolyzed and condensed under a suitable condition in a solvent containing water to give a spherical shape. In addition, it precipitates as composite particles having a very sharp particle size distribution to form a suspension.
Here, suitable conditions are, for example, preferably 20% by weight or less for the raw material concentration, 50% by weight or more for the water concentration, and 10% by weight or less for the catalyst concentration with respect to the obtained suspension. .

The average particle size of the produced composite particles is 50 to 99.9 for water concentration, catalyst concentration, organic solvent concentration, raw material concentration, raw material addition time, temperature and seed particle concentration, respectively.
9% by weight, 0.01 to 10% by weight, 0 to 50% by weight,
0.1 to 30% by weight, 0.001 to 500 hours, 0-1
By setting the temperature to 00 ° C. and 0 to 10% by weight, the average particle size can be within the range of the above-mentioned first spacer. The coefficient of variation of the particle diameter of the composite particles to be produced is the coefficient of variation of the particle diameter of the above-mentioned first spacer by setting the water concentration, the catalyst concentration, and the organic solvent concentration within the above ranges. Can be in range.

Then, the composite particles thus produced are isolated from the above suspension by a conventionally known method such as filtration, centrifugation, concentration under reduced pressure, etc., and then 100 ° C. or higher, 100
The organic-inorganic composite particles having appropriate hardness and mechanical recoverability are obtained by performing heat treatment for drying and firing at a temperature of 0 ° C. or lower, preferably 300 ° C. or higher and 900 ° C. or lower. A second spacer of the invention is obtained. This composite particle contains, as a main component, a polysiloxane having in its molecule an organosilicon in which at least one carbon atom in an organic group is directly chemically bonded to a silicon atom. 10
In the heat treatment at a temperature lower than 0 ° C., the following formula (4) present in the siloxane unit represented by the formula (2)

[0045]

[Chemical 5]

Since the dehydration condensation reaction between the silanol groups represented by the above does not sufficiently occur, the required hardness cannot be obtained,
That is, the 10% compressive elastic modulus of the particles is 350 kg / mm ² or more, and the residual displacement after 10% deformation is not 5% or less. Further, the heat treatment at a temperature higher than 1000 ° C. causes the decomposition of the organic groups to be remarkable, so that the necessary mechanical restoration cannot be obtained, that is, the residual displacement after 10% deformation of the particles is 0 to 0.
It does not reach 5%, and is too hard so that the 10% compression modulus of the particles exceeds 3000 kg / mm ² . Further, the atmosphere during the heat treatment can be used without any limitation, but in order to suppress the decomposition of the organic group and obtain the necessary mechanical restoring property, it is more preferable that the oxygen concentration in the atmosphere is 10% by volume or less. preferable. When the heat treatment temperature is in the range of 350 ° C. to 1000 ° C., in order to obtain the first spacer, the oxygen concentration in the atmosphere during the heat treatment is preferably 10% by volume or less, and the heat treatment temperature is 100 to 350 ° C. Within the range, the first spacer is generated even in the air.

When the second spacer is formed, the ratio of the organic groups in the composite particles is set within the above range (first range) by selecting the kind and amount of the above-mentioned raw materials, the heat treatment temperature / time and the oxygen concentration in the atmosphere. It can be arbitrarily manufactured within the range described in the description of the spacer of (1). At the time of hydrolysis, condensation, or heat treatment, another compound capable of reacting with the hydrolyzable / condensable silicon compound having a reactive group as described above to form a chemical bond may coexist. In this case, for example, a conventionally known dye,
Coloring compounds such as pigments may coexist.

The spacer for a liquid crystal display panel of the present invention obtained as described above is used for improving the dispersibility on the electrode substrate or for suppressing the abnormal alignment of the liquid crystal substance on the surface of the spacer. Or for fixing the spacer so as not to move on the electrode substrate, or for other purposes, surface modification with a coupling agent, surface modification with the aforementioned organometallic compound or inorganic compound,
It may be used as a spacer by subjecting a conventionally known surface modification treatment such as surface modification with another organic compound. For example, the surface treatment method described in JP-A-62-269933 is adopted. In this publication, when the silica particles produced by the sol-gel method are applied to a spacer for a liquid crystal display panel, in order to improve the sprayability of the spacer on the electrode substrate, or the abnormality of the liquid crystal substance on the spacer surface. In order to suppress the occurrence of orientation, the spacers are surface-treated with alcohols, coupling agents and the like.

The obtained spacer for liquid crystal display panel of the present invention
-C bond and white pigment in the composite particles constituting the
The sun unit is a conventional unit such as FT-IR, NMR, ESCA.
Confirmed by known methods, and also occupy the composite particles in the organic particles
The ratio of groups shall be the ratio of total carbon atoms determined by elemental analyzer.
It is measured quantitatively. The liquid crystal display panel of the present invention is
In the liquid crystal display board of, instead of the conventional spacer,
The liquid crystal display panel spacer of the present invention is interposed between the electrode substrates.
The same as the particle size of the spacer,
Have approximately the same clearance distance. Of used spacers
Quantity is usually 40-100 pieces / mm², Preferably 40-8
0 / mm ²And compared to conventional organic particle spacers
It is about 10% less, and the
The area is reduced, and impurities such as ions and molecules are swallowed.
The amount eluted from the inside of the pacer into the liquid crystal layer is also reduced. This
Therefore, the contrast is high, the roughness is reduced, and the
It is expected that the display quality will be improved.

For the liquid crystal display panel of the present invention, other than the spacer, such as an electrode substrate, a sealing material, a deflecting plate, and a reflecting plate, those similar to the conventional one can be used in the same manner. The liquid crystal substance may be a conventionally used one, for example, biphenyl-based, phenylcyclohexane-based, Schiff base-based, azo-based, azoxy-based, benzoic acid ester-based, terphenyl-based, cyclohexylcarboxylic acid ester-based, biphenyl. Liquid crystals such as cyclohexane, pyrimidine, dioxane, cyclohexylcyclohexane ester, cyclohexylethane, and cyclohexene can be used.

In the present invention, as a method for producing a liquid crystal display panel using the spacer for a liquid crystal display panel of the present invention as a spacer, the spacer of the present invention is applied to one of two electrode substrates by a wet method or After being uniformly dispersed by a dry method, the spacer of the present invention is dispersed in an adhesive seal material such as an epoxy resin, and then the adhesive seal portion of the other electrode substrate is coated with a means such as screen printing. Apply moderate pressure, 100 ~
After heating and curing the adhesive sealing material by heating at 180 ° C. for 1 to 60 minutes or irradiation with ultraviolet rays having an irradiation dose of 40 to 300 mJ / cm ² , liquid crystal is injected and the injection part is sealed, A method for obtaining a liquid crystal display plate can be mentioned,
The present invention is not limited by the method of manufacturing the liquid crystal display panel.

The liquid crystal display panel of the present invention is used in the same applications as conventional ones, for example, as an image display device for televisions, personal computers, word processors and the like.

[0053]

The first spacer of the present invention is composed of organic-inorganic composite particles containing the above polysiloxane as a main component, and has the inorganic constitutional unit represented by the above formula (2) and the organic silicon at the same time. In addition, it is a particle that has both a large hardness, which is a characteristic of an inorganic substance, and a high mechanical restoration property, which is a characteristic of an organic substance. That is, the composite particles are
As a measure of hardness, 10% compression elastic modulus 350 to 300
It has 0 kg / mm ² and 0 to 5% residual displacement after 10% deformation as a measure of mechanical resilience, and has an average particle size of 0.5 to 50 μm suitable as a gap distance. It is a uniform particle having a variation coefficient of 20% or less and a uniform particle diameter.

The second spacer of the present invention has the general formula (1)

[0055]

[Chemical 6]

(Wherein R ¹ , R ² , and m are as described above) and at least one hydrolyzable and condensable silicon compound selected from the group consisting of compounds and derivatives thereof (provided that they are independent. The silicon compound that can be used is only a compound selected from the group consisting of compounds represented by m = 1 in formula (1) and derivatives thereof,
The two or more silicon compounds used in combination include a compound selected from the group consisting of a compound represented by m = 1 in Formula (1) and a derivative thereof and a compound represented by m = 0 in Formula (1) and a derivative thereof. It is necessary to include both and / or one of the compounds selected from the group consisting of ] Hydrolyzable / condensable metal compound containing
Since it is heat-treated within the range, it has both a large hardness, which is a characteristic of an inorganic material, and a high mechanical resilience, which is a characteristic of an organic material, and has a particle diameter suitable as a gap distance and a uniform particle diameter. Particles. The second spacer is
Preferably, 10% compression elastic modulus is 3 as a measure of hardness.
The average particle size is 50 to 3000 kg / mm ^2, and the residual displacement is 0 to 5% after 10% deformation as a measure of mechanical resilience, and the average particle size is 0.5 to 50 μm, which is suitable for the gap distance. It is composed of composite particles having a diameter variation coefficient of 20% or less.

In the liquid crystal display panel of the present invention, since the spacer for liquid crystal display panel of the present invention is interposed between the electrode substrates, physical damage caused by pressing during manufacturing, low temperature foaming, and image unevenness are unlikely to occur. Moreover, since the number of spacers interposed between the electrode substrates is reduced, the area of a portion where no image is formed is reduced and the amount of impurities eluted into the liquid crystal layer is reduced. Therefore, display quality is improved, such as improved contrast and reduced roughness.

[0058]

EXAMPLES Examples of the present invention and comparative examples outside the scope of the present invention will be shown below, but the present invention is not limited to the following examples. The liquid crystal display panel in the following examples was produced by the following method. As shown in Fig. 1, first, 300mm
After forming an electrode (for example, a transparent electrode) 5 and a polyimide alignment film 4 on the lower glass substrate 11 of × 345 mm × 1.1 mm, rubbing is performed on the lower electrode substrate 110,
10 parts by volume of methanol, 40 parts by volume of isopropanol,
Spacers of the present invention (in this case, in-plane spacers) 8 uniformly dispersed so as to be 1% by weight in a mixed solvent of 50 parts by volume of water were sprayed for 1 to 10 seconds. Next, a spacer (spacer in this case) 3 of the present invention dispersed in the epoxy resin adhesive sealing material 2 so as to be 30% by volume was prepared as 300 mm × 345 mm × 1.
The electrode (for example, transparent electrode) 5 and the polyimide alignment film 4 were formed on the upper glass substrate 12 having a thickness of 1 mm, and the upper electrode substrate 120, which was rubbed, was screen-printed on the adhesive seal portion. Finally, the upper and lower electrode substrates 120, 11
0 is bonded via the spacer 8 of the present invention so that the electrodes 5 and 5 and the alignment films 4 and 4 face each other.
After applying a pressure of / cm ² and heating at a temperature of 150 ° C. for 30 minutes to heat and cure the adhesive sealing material 2, the gap between the two electrode substrates 120 and 110 is evacuated and then brought to atmospheric pressure. Thus, the liquid crystal 7 in which a liquid crystal substance such as biphenyl-based or phenylcyclohexane-based is mixed is injected from the injection part until the gap is filled with the liquid crystal 7, and the injection part is sealed, Upper and lower glass substrates 12,
A PVA (polyvinyl alcohol) -based polarizing film 6 was attached to the outside of 11 to form a liquid crystal display plate.

In each of the evaluation methods of the obtained liquid crystal display panels, in the image display state, the presence or absence of image display after holding for 1000 hours at −45 ° C. for low temperature foaming, room temperature ( The presence or absence of them at 25 ° C.) was visually observed. (Example 1) In a 2 liter glass reactor equipped with a stirrer, a dropping port and a thermometer, 307 parts by weight of methanol, 6 parts by weight of 25% ammonia water, and 1225 parts by weight of water were uniformly mixed. This mixed solution was adjusted to 20 ± 0.5 ° C. and uniformly stirred at 100 rpm, 60 parts by weight of methyltrimethoxysilane was added dropwise from a dropping port over 6 hours. After the dropwise addition, stirring was continued for 1 hour to carry out hydrolysis and condensation to obtain a suspension (A) of condensate hydrate particles of methyltrimethoxysilane. The suspension (A) was subjected to solid-liquid separation by filtration, and the cake obtained was washed with methanol three times, and the obtained solid content powder was dried in a vacuum dryer at 100 ° C. for 3 hours. Then, in a nitrogen atmosphere, 3
Heat treatment at 50 ° C for 3 hours gives an average particle size of 1.81.
Organic-inorganic composite particles having a micrometer and a variation coefficient of 7.6% were obtained.

When the hardness and mechanical recoverability of the obtained composite particles were evaluated by the above-mentioned method, the 10% compression modulus was 711 kg / mm ² , and the residual displacement after 10% deformation was 2.5%.
Met. In addition, by FTIR, Si-
The presence of CH ₃ bonds and siloxane units was confirmed. Further, the ratio of the organic groups in the composite particles as determined by elemental analysis was 13.3% by weight, which is the amount of the organic groups expressed as the weight of all carbon atoms.

Using this composite particle, a B5-size ferroelectric liquid crystal display panel was prepared by a known method, and was dispersed on an existing organic particle spacer (Nippon Shokubai Co., Ltd. Eposter GP-H). It was possible to reduce the number of particles by 10% or more, and it was possible to manufacture a liquid crystal display panel which did not cause low-temperature foaming or image unevenness which occurs when silica calcined product particles or uncalcined silica particles obtained by the sol-gel method are used.

Example 2 In Example 1, 154 parts by weight of methanol and 153 parts by weight of n-butanol were used in place of 307 parts by weight of methanol, 350
Organic-inorganic composite particles having an average particle size of 6.84 μm and a coefficient of variation of 5.9% were obtained in the same manner as in Example 1 except that the heat treatment was performed at 750 ° C. for 1 hour instead of the heat treatment at 3 ° C. for 3 hours. Got

The 10% compression modulus of the obtained composite particles was 750 kg / mm ² , and the residual displacement after 10% deformation was 3.1%. In addition, Si-C was included in the composite particles by FTIR.
The presence of H ₃ bonds and siloxane units was confirmed, and the ratio of the organic groups in the composite particles by elemental analysis was 12.1% by weight in terms of the amount of the organic groups in terms of the weight of all carbon atoms. Using this composite particle, a B5 version STN is produced by a known method.
When a (abbreviation of Super Twisted Nematic) type liquid crystal display panel was produced, the same results as in Example 1 were obtained.

Example 3 In Example 1, 154 parts by weight of methanol and 153 parts by weight of n-butanol were used instead of 307 parts by weight of methanol, and tetraethoxysilane 17 was used instead of 60 parts by weight of methyltrimethoxysilane. Parts by weight and methyltrimethoxysilane 4
An average particle diameter of 4.47 μm and a coefficient of variation of 6. were obtained in the same manner as in Example 1 except that 3 parts by weight was used, and heat treatment was performed at 600 ° C. for 2 hours instead of 350 ° C. for 3 hours. 8% of organic-inorganic composite particles were obtained. Here, since it is 80 mol% of methyltrimethoxysilane and 20 mol% of tetraethoxysilane, n in the above formula (3) is 0.8.

The 10% compression modulus of the obtained composite particles is
1606 kg / mm²Residual displacement after 10% deformation is 4.7%
Met. In addition, by FTIR, Si-
CH ₃The presence of bonds and siloxane units was confirmed,
The ratio of the organic groups in the composite particles obtained by precipitation depends on the amount of the organic groups.
The weight of all carbon atoms was 9.2% by weight. this
B5 plate size TFT by a known method using composite particles
(Abbreviation of Thin Film Transistor) type LCD panel
However, the same results as in Example 1 were obtained, and the pixel
No defects were found.

Example 4 In Example 2, instead of heat treatment at 750 ° C. for 1 hour in a nitrogen atmosphere, nitrogen 95% was used.
2 at 450 ° C in a mixed atmosphere of 5% by volume of oxygen and 5% by volume of oxygen
In the same manner as in Example 2 except that the heat treatment was performed for a time, organic-inorganic composite particles having an average particle diameter of 6.15 μm and a coefficient of variation of 6.7% were obtained.

The 10% compression modulus of the obtained composite particles is
1440 kg / mm²Residual displacement after 10% deformation is 3.8%
Met. In addition, by FTIR, Si-
CH ₃The presence of bonds and siloxane units was confirmed,
The ratio of the organic groups in the composite particles obtained by precipitation depends on the amount of the organic groups.
The weight of all carbon atoms was 10.1% by weight. This
By using a known method using the composite particles of
When an N-type liquid crystal display panel was produced, the same result as in Example 2 was obtained.
The fruit was obtained.

Example 5 In Example 1, 154 parts by weight of methanol and 153 parts by weight of n-butanol were used in place of 307 parts by weight of methanol, and ethyltrimethoxysilane was replaced by 60 parts by weight of methyltrimethoxysilane. Using 60 parts by weight, 3 at 350 ° C
The average particle size was 1. 1 in the same manner as in Example 1 except that heat treatment was performed at 750 ° C. for 3 hours instead of heat treatment for 3 hours.
Organic-inorganic composite particles having a diameter of 97 μm and a coefficient of variation of 6.9% were obtained.

The 10% compressive elastic modulus of the obtained composite particles was 811 kg / mm ² , and the residual displacement after 10% deformation was 3.2%. In addition, Si-C was included in the composite particles by FTIR.
H ₂ - is the presence confirmation of the binding and siloxane units, the proportion of organic groups in the composite particles in accordance with elemental analysis, was 12.0 wt% represents the amount of organic groups by weight of the total carbon atoms. When a B5 size ferroelectric liquid crystal display panel was produced using the composite particles by a known method, the same results as in Example 1 were obtained.

Example 6 In Example 3, 600 ° C.
In the same manner as in Example 3 except that the heat treatment was carried out in air at 200 ° C. for 5 hours instead of the heat treatment for 2 hours.
Organic matter with an average particle size of 4.55 μm and a coefficient of variation of 6.8%
Inorganic composite particles were obtained. 10% of the obtained composite particles
The compression modulus was 630 kg / mm ² , and the residual displacement after 10% deformation was 2.3%. The presence of Si—CH ₃ bonds and siloxane units in the composite particles was confirmed by FTIR, and the proportion of organic groups in the composite particles by elemental analysis was calculated by expressing the amount of organic groups by the weight of all carbon atoms. It was 14.3% by weight.

When a B5 size TFT type liquid crystal display panel was produced by a known method using the composite particles, the same results as in Example 1 were obtained and no pixel defect was observed. (Comparative Example 1) Organic-inorganic composite particles were obtained in the same manner as in Example 2, except that the heat treatment was performed at 80 ° C for 2 hours instead of the heat treatment at 750 ° C for 1 hour.

The 10% compressive elastic modulus of the obtained composite particles was 312 kg / mm ² , and the residual displacement after 10% deformation was 2.0%. The ratio of the organic groups in the composite particles as determined by elemental analysis was 18% by weight, which is the amount of the organic groups expressed as the weight of all carbon atoms. When a B5 plate-sized STN type liquid crystal display panel was produced using this composite particle by a known method, the same number of dispersed particles as the existing organic polymer particle spacer was required.

Comparative Example 2 600 ° C. in Example 3
Particles were obtained in the same manner as in Example 3 except that the heat treatment was performed at 1150 ° C for 1 hour instead of the heat treatment for 2 hours. The 10% compression modulus of the obtained particles is 3380 kg / mm.
² , The residual displacement after 10% deformation was 6.4%. The proportion of the organic groups in the particles as determined by elemental analysis was 1% by weight, which is the amount of the organic groups expressed as the weight of all carbon atoms.

A B5 plate size TFT type liquid crystal display panel was prepared by using these particles by a known method.
Pixel defects due to FT disconnection occurred, and the mechanical recovery of particles was not sufficient, resulting in image unevenness. The number of spacers according to the present invention dispersed in the plane of the liquid crystal display panel obtained in the above-mentioned embodiment is within an arbitrary 1 mm ² in each of the nine areas by dividing the dispersion plane into three equal parts vertically and horizontally. The number of spacers of the present invention was counted by an optical microscope, and the average value of the number of 9 areas in total was taken as the number of scattered particles. The results were as follows. Example 1 ... spraying number 73 / mm ² Example 2 ... spraying number 70 / mm ² Example 3 ... spraying number 69 / mm ² Example 4 ... spraying number 68 / mm ² Example 5 ... spraying number 69 / mm ² Example 6 ... Spreading number 66 / mm ² (Comparative Example 3) Using the existing organic particle spacer described in Example 1, a STN type liquid crystal display plate of B5 size was prepared by a known method. As a result, image unevenness appeared remarkably and it could not be used as a liquid crystal display panel. At this time, the number of scattered spacers was 66 / mm ² according to the above counting method.

[0075]

The spacer for a liquid crystal display panel of the present invention comprises:
An organic-inorganic composite particle having a very uniform particle size and a structure in which an organic group and a siloxane unit represented by the above formula (2) are uniformly distributed inside and on the surface of the particle. Therefore, it has hardness between the calcined silica particles and the organic polymer particles, and high mechanical recoverability. Therefore, by using the spacer for a liquid crystal display panel of the present invention, it is possible to prevent damage to the electrode substrate surface, occurrence of low-temperature foaming, occurrence of image unevenness, increase in manufacturing cost, deterioration of various display performance, and Even if the number of sprayed particles is drastically reduced as compared with the organic polymer particles, it is possible to maintain a strictly constant gap distance, and it is possible to manufacture a high-performance liquid crystal display panel with excellent image quality.

In the liquid crystal display panel of the present invention, since the gap distance between the electrode substrates is set by using the spacer for liquid crystal display plate of the present invention, the surface of the electrode substrate is scratched, low temperature foaming occurs, and image unevenness occurs. In addition, the manufacturing cost is not increased, various display performances are not deteriorated, and even if the number of sprayed particles is significantly reduced as compared with the conventional organic polymer particles, a strictly constant gap distance can be maintained, and the image quality can be improved. It has excellent high performance.

[Brief description of drawings]

FIG. 1 is a partial cross-sectional view showing an example of a liquid crystal display panel.

[Explanation of symbols]

 2 Adhesive Sealing Material 3 Seal Spacer 4 Alignment Film 5 Electrode 6 Polarizing Film 7 Liquid Crystal 8 In-plane Spacer 11 Lower Glass Substrate 12 Upper Glass Substrate 110 Lower Electrode Substrate 120 Upper Electrode Substrate

Claims (4)

[Claims] 1. A spacer for a liquid crystal display panel, which comprises organic-inorganic composite particles whose main component is polysiloxane having in its molecule an organic silicon in which at least one carbon atom in an organic group is directly chemically bonded to a silicon atom. And the 10% compression modulus of the particles is 350 to 3000 kg / mm ² ,
The residual displacement after 10% deformation is 0 to 5%, and the average particle size is 0.
A spacer for a liquid crystal display panel, which has a coefficient of variation of 5 to 50 μm and a particle diameter of 20% or less. 2. The following general formula (1): (In the formula, R ¹ has a carbon number of 1 to 1 which may have a substituent.
A monovalent group selected from the group consisting of an alkyl group having 10 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an unsaturated aliphatic residue having 2 to 10 carbon atoms, R ² is a hydrogen atom, and 1 to 5 carbon atoms. 1 selected from an alkyl group and an acyl group having 2 to 5 carbon atoms
A valent group, m is an integer of 0 to 3. When m is 2, two R ¹ 's may be different from each other or the same. When m is 3, three R ¹ 's may be different from each other, or two or more R ¹ 's may be the same. When 4-m is 2, two OR ²
May be different from each other or may be the same. 4-m is 3
In the case of, three OR ^{2 s} may be different from each other or two or more may be the same. If 4-m is 4, then four OR ²
May be different from each other, or two or more may be the same. ) At least one hydrolyzable / condensable silicon compound selected from the group consisting of a compound represented by the formula (1) and a derivative thereof (wherein the silicon compound which can be used alone is Only a compound selected from the group consisting of its derivatives,
The two or more silicon compounds used in combination include a compound selected from the group consisting of a compound represented by m = 1 in Formula (1) and a derivative thereof and a compound represented by m = 0 in Formula (1) and a derivative thereof. It is necessary to include both and / or one of the compounds selected from the group consisting of ] Hydrolyzable / condensable metal compound containing
Spacer for liquid crystal display panel that is heat-treated in the range of. 3. The spacer for a liquid crystal display panel according to claim 2, wherein the heat treatment is performed in an atmosphere having an oxygen concentration of 10% by volume or less. 4. A liquid crystal display panel comprising the spacer according to claim 1 as a spacer interposed between electrode substrates.